Benzylidene pyrazolones, production and use thereof

ABSTRACT

Benzylidenepyrazolones of the formula I,Useful as herbicides.

This application is a 371 of PCT/EP98/07099 filed Nov. 6, 1998.

The present invention relates to benzylidenepyrazolones of the formula I

where the substituents and the index n have the following meanings:

R¹ is unsubstituted or substituted C₁-C₆-alkyl;

R² is unsubstituted or substituted C₁-C₆-alkyl, unsubstituted orsubstituted C₁-C₆-alkoxy, halogen, nitro, cyano;

R³ is hydrogen, halogen, nitro, cyano, a group NR⁵R⁶, OCOR⁵, NR⁵COR⁶,CO₂R⁵, —COSR⁵, —CONR⁵R⁶, C₁-C₄-alkoxyiminoalkyl, C₁-C₆-alkylcarbonyl,unsubstituted or substituted C₁-C₆-alkyl, unsubstituted or substitutedC₁-C₆-alkoxy, unsubstituted or substituted C₁-C₆-alkylthio,unsubstituted or substituted C₂-C₆-alkenyl, unsubstituted or substitutedC₂-C₆-alkynyl, unsubstituted or substituted phenyl, unsubstituted orsubstituted phenoxy, an unsubstituted or substituted 5- or 6-memberedsaturated or unsaturated heterocycle which may contain up to 4 nitrogenatoms and/or up to 2 oxygen or sulfur atoms as ring members;

R⁴ is C₁-C₆-alkyl, C₁-C₄-haloalkyl;

or

R³ and R⁴ form an optionally substituted saturated or unsaturated 2- or3-membered bridge which may contain a sulfur atom which may be oxidizedto give sulfoxide or sulfone;

R⁵ is hydrogen or unsubstituted or substituted C₁-C₆-alkyl;

R⁶ is unsubstituted or substituted C₁-C₆-alkyl;

R⁷ is hydrogen, C₁-C₆-alkyl or C₁-C₄-haloalkyl;

n is 0, 1 or 2;

x is hydrogen, chlorine or bromine;

where the compounds claimed may be present both in the trans and in thecis form or as a mixture of these isomers.

Furthermore, the present invention relates to compositions whichcomprise the compounds of the formula I, and to the use of the compoundsI and of compositions comprising them for controlling harmful plants, tonovel benzoylpyrazoles of the formula II and to a process for preparingthe compounds I and II.

Herbicidally active 4-benzoylpyrazoles are disclosed in the literature,for example in EP-A 282 944 or WO 96/26206. However,4-benzoyl-5-chloropyrazoles have hitherto not been described. In EP-A282 944, it is only mentioned in a general way that the reaction of4-benzoyl-5-hydroxypyrazoles with acyl halides should lead to4-benzoyl-5-chloropyrazoles.

Benzylidenepyrazolones, some of which have herbicidal activity, aredisclosed in U.S. Pat. No. 4,382,948 and JP 61268670. All the structuresof the prior art have a very specific substitution pattern in the phenylmoiety of the benzylidenepyrazolone: in the position para to the methynebridge, for example, there is in each case a hydrogen or halogen atom ora trifluoromethyl or nitro group.

However, the herbicidal properties of the prior art compounds and theircompatibility with crop plants are not entirely satisfactory.

It is an object of the present invention to provide novel, in particularherbicidally active, compounds having improved properties.

We have found that this object is achieved by the benzylidenepyrazolonesof the formula I according to the invention and by their herbicidalactivity.

The present invention also provides stereoisomers of the compounds ofthe formula I. Both pure stereoisomers and mixtures thereof areincluded.

The compounds of the formula I may be present as cis or trans isomersand may contain, depending on the substitution pattern, one or morechiral centers, in which case they may also be present as mixtures ofenantiomers or diastereomers. The invention provides both the pureisomers, enantiomers or diastereomers and mixtures thereof.

Benzylidenepyrazolones of the formula I and benzoylpyrazoles of theformula II according to the invention can be prepared as describedbelow.

Benzylidenepyrazolones of the formula Ia (X=hydrogen) can be synthesizedby Knoevenagel condensation of pyrazolones of the formula III, in whichthe radicals R¹ and R⁷ are as defined above, and a substitutedbenzaldehyde of the formula IV, in which the radicals R² to R⁴ are asdefined above, similarly to the method described in U.S. Pat. No.4,382,948.

Furthermore, the compounds Ia are obtainable for example by reductivedehalogenation from compounds of the formula I in which X is bromine.

Benzylidenepyrazolones Ib (X=bromine or chlorine) can be prepared fromthe compounds Ia described above by halogenation with bromine orchlorine and subsequent dehydrohalogenation in the presence of base.

The benzylidenepyrazolones Ib are preferably obtained from ketones ofthe formula V, which are either known or which can be prepared similarlyto known compounds (see DE-A 19709118.0 and WO 96/26200), by reactionwith acyl halides.

Suitable acyl halides are, for example, the halides of sulfuric acid,carbonic acid and phosphoric acid. For the exchange with chlorine,preference is given to using thionyl chloride, phosgene, phosphoruspentachloride and particularly preferably phosphorus oxychloride. Forthe exchange with bromine, preference is given to using phosphorusoxybromide.

The reaction can be carried out in a customary manner, with or withoutsolvent or with a solvent which is inert under the reaction conditions.Generally, it is possible to control the selectivity of the reaction byaddition of a base of low nucleophilicity such as, for example,pyridine, dimethylaminopyridine or dimethylformamide.

The reaction temperature is generally from 0° C. to 200° C., preferablyfrom 50° C. to 140° C.

In this reaction, a mixture of both isomers with respect to the newlyformed double bond may be obtained. In this case, the isomers can beseparated, if required (for example by crystallization, extraction orchromatography).

A byproduct of this reaction are the compounds II which, depending onthe substitution pattern and the way in which the reaction is carriedout, may be obtained in smaller, similar or higher proportions. Many ofthese compounds are novel, and they are of considerable interest asprecursors for herbicidally active compounds (see for example EP-A 282944).

The organic moieties mentioned for the substituents R¹-R⁷ or as radicalson phenyl rings or heterocycles represent collective terms for lists ofthe individual group members. All hydrocarbon chains, ie. all alkyl,haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkylcarbonyl, alkenyl,alkynyl moieties may be straight-chain or branched. Unless statedotherwise, halogenated substituents preferably carry one to fiveidentical or different halogen atoms. Halogen is in each case fluorine,chlorine, bromine or iodine.

Examples of other meanings are:

C₁-C₄-alkyl and the alkyl moieties of other radicals such as, forexample, C₁-C₄-alkoxy, C₁-C₄-alkylcarbonyl, C₁-C₄-alkylthio: methyl,ethyl, n-propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyland 1,1-dimethylethyl;

C₁-C₆-alkyl and the alkyl moieties of other radicals such as, forexample, C₁-C₆-alkoxy, C₁-C₆-alkylcarbonyl, C₁-C₆-alkylthio: C₁-C₄-alkylas mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1-ethyl-1-methylpropyl and 1-ethy-1-3-methylpropyl;

C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, ie. for example chloromethyl, dichloromethyl, trichloromethyl,fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl,dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl,2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl,2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl,1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl,1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyland nonafluorobutyl;

C₁-C₄-haloalkoxy: a C₁-C₄-alkoxy radical as mentioned above which ispartially or fully substituted by fluorine, chlorine, bromine and/oriodine, ie. for example fluoromethoxy, difluoromethoxy,trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy,2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy,2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy,3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy,3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy,2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy,2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy,1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy,1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy,4-bromobutoxy and nonafluorobutoxy;

C₂-C₆-alkenyl: ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl,buten-1-yl, buten-2-yl, buten-3-yl, 1-methyl-prop-1-en-1-yl,2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl,penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl,1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl,1-methylbut-2-en-1-yl, 2-methyl-but-2-en-1-yl, 3-methylbut-2-en-1-yl,1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl,1,1-dimethyl-prop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl,1,2-dimethyl-prop-2-en-1-yl, 1-ethylprop-1-en-2-yl,1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl,hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl,2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,1-methyl-pent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl,4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methyl-pent-3-en-1-yl,3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl,2-methylpent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 4-methylpent-4-en-1-yl,1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl,1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl,1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl,2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl,3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl,1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,2-ethylbut-1-en-1-yl, 2-ethyl-but-2-en-1-yl, 2-ethylbut-3-en-1-yl,1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,1-ethyl-2-methyl-prop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;

C₂-C₆-alkynyl: ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl,but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl, pent-1-yn-1-yl,pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl,pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl,3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl,hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl,hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl,3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yland 4-methyl-pent-2-yn-5-yl;

C₃-C₆-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

an unsubstituted or substituted 5- or 6-membered saturated orunsaturated heterocycle which may contain up to 4 nitrogen atoms and/orup to 2 oxygen or sulfur atoms as ring members, such as2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl,3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl,4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl,4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl,4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl,5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl,2-imidazolidinyl, 4-imidazolidinyl, 1,2,4-oxadiazolidin-3-yl,1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl,1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl,1,3,4-triazolidin-2-yl, 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl,2,3-dihydrofuran-4-yl, 2,3-dihydrofuran-5-yl, 2,5-dihydrofuran-2-yl,2,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl,2,3-dihydrothien-4-yl, 2,3-dihydrothien-5-yl, 2,5-dihydrothien-2-yl,2,5-dihydrothien-3-yl, 2,3-dihydropyrrol-2-yl, 2,3-dihydropyrrol-3-yl,2,3-dihydropyrrol-4-yl, 2,3-dihydropyrrol-5-yl, 2,5-dihydropyrrol-2-yl,2,5-dihydropyrrol-3-yl, 2,3-dihydroisoxazol-3-yl,2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl,4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl,4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazol-3-yl,2,5-dihydroisoxazol-4-yl, 2,5-dihydroxazol-5-yl,2,3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl,2,3-dihydroisothiazol-5-yl, 4,5-dihydroisothiazol-3-yl,4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl,2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl,2,5-dihydroisothiazol-5-yl, 2,3-dihydropyrazol-3-yl,2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl,4,5-dihydropyrazol-5-yl, 2,5-dihydropyrazol-3-yl,2,5-dihydropyrazol-4-yl, 2,5-dihydropyrazol-5-yl,2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl,4,5-dihydrooxazol-2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl,2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5-dihydrooxazol-5-yl,2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl,2,3-dihydrothiazol-5-yl, 4,5-dihydrothiazol-2-yl,4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl,2,5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl,2,5-dihydrothiazol-5-yl, 2,3-dihydroimidazol-2-yl,2,3-dihydroimidazol-4-yl, 2,3-dihydroimidazol-5-yl,4,5-dihydroimidazol-2-yl, 4,5-dihydroimidazol-4-yl,4,5-dihydroimidazol-5-yl, 2,5-dihydroimidazol-2-yl,2,5-dihydroimidazol-4-yl, 2, 5dihydroimidazol-5-yl, 2-morpholinyl,3-morpholinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl,3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl,2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl,5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl,1,3,5-tetrahydrotriazin-2-yl, 1,2,4-tetrahydrotriazin-3-yl,1,3-dihydrooxazin-2-yl, 1,3-dithian-2-yl, 2-tetrahydropyranyl,3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothiopyranyl,3-tetrahydrothiopyranyl, 4-tetrahydrothiopyranyl, 1,3-dioxolan-2-yl,3,4,5,6-tetrahydropyridin-2-yl, 4H-1,3-thiazin-2-yl, 4H-,1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 1,3-dihydrooxazin-2-yl, 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl,4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl,5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 2-thiazolyl, tetrazol-5-yl, tetrazol-1-yl,4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl,1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl,1,2,4-thiadiazol-5-yl, 1,2,4-triazol-3-yl, 1,3,4-oxadiazol-2-yl,1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl,4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl,5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl,1,2,4,5-tetrazin-3-yl.

With respect to the herbicidal activity of the benzylidenepyrazoles I,particular preference is given to the following meanings of thesubstituents, in each case either alone or in combination:

R¹ is C₁-C₄-alkyl or C₁-C₄-haloalkyl;

R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,halogen, nitro, cyano;

R³ is hydrogen, halogen, nitro, cyano, a group NR⁵R⁶, OCOR⁵, NR⁵COR⁶,CO₂R⁵, —COSR⁵, —CONR⁵R⁶, C₁-C₄-alkoxyiminoalkyl, C₁-C₄-alkylcarbonyl,unsubstituted or halogen-, C₁-C₄-alkoxy- or phenyl-substitutedC₁-C₄-alkyl, where the phenyl ring for its part may be substituted byhalogen, C₁-C₂-alkyl or C₁-C₂-alkoxy, unsubstituted or halogen-,C₁-C₄-alkoxy- or phenyl-substituted C₁-C₄-alkoxy, where the phenyl ringfor its part may be substituted by halogen, C₁-C₂-alkyl or C₁-C₂-alkoxy,unsubstituted or halogen-, C₁-C₄-alkoxy- or phenyl-substitutedC₁-C₄-alkylthio, where the phenyl ring for its part may be substitutedby halogen, C₁-C₂-alkyl or C₁-C₂-alkoxy, unsubstituted or C₁-C₄-alkyl-or halogen-substituted C₂-C₆-alkenyl or C₂-C₆-alkynyl, unsubstituted orC₁-C₄-alkyl-C₁-C₄-alkoxy-, C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-,halogen-, phenyl-, cyano-, alkoxycarbonyl- or nitro-substituted phenylor phenoxy, an unsubstituted or C₁-C₄-alkyl-, C₁-C₄-alkoxy-,C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy-, halogen-, phenyl-, cyano- ornitro-substituted 5- or 6-membered saturated or unsaturated heterocyclewhich may contain up to 4 nitrogen atoms and/or up to 2 oxygen or sulfuratoms as ring members, selected from the group consisting oftetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl,isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl,imidazolidinyl, 1,2,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl,1,2,4-triazolidinyl, 1,3,4-oxadiazolidinyl, 1,3,4-thiadiazolidinyl,1,3,4-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl,2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-dihydropyrrolyl,2,5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl,2,5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl,4,5-dihydroisothiazolyl, 2,5-dihydroisothiazolyl, 2,3-dihydropyrazolyl,4,5-dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl,4,5-dihydrooxazolyl, 2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl,4,5-dihydrothiazolyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl,4,5-dihydroimidazolyl, 2,5-dihydroimidazolyl, morpholinyl, piperidinyl,tetrahydropyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl,1,3,5-tetrahydrotriazinyl, 1,2,4-tetrahydrotriazinyl,1,3-dihydrooxazinyl, 1,3-dithianyl, tetrahydropyranyl,tetrahydrothiopyranyl, 1,3-dioxolanyl,1,1-dioxo-2,3,4,5-tetrahydrothienyl, 1,3-dihydrooxazinyl, furyl,thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl,thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl,1,2,4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl,1,3,4-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl;

R⁴ is C₁-C₆-alkyl, C₁-C₄-haloalkyl;

or

R³ and R⁴ form an unsubstituted or substituted saturated or unsaturated2- or 3-membered bridge which may contain a sulfur atom which may beoxidized to the sulfoxide or sulfone;

R⁵ is hydrogen, C₁-C₄-alkyl which is unsubstituted or substituted byhalogen, C₁-C₄-alkoxy or phenyl, where the phenyl ring may carry one tofive substituents selected from the group consisting of halogen,C₁-C₂-alkyl and C₁-C₂-alkoxy;

R⁶ is C₁-C₄-alkyl which is unsubstituted or substituted by halogen,C₁-C₄-alkoxy or phenyl, where the phenyl ring may carry one to fivesubstituents selected from the group consisting of halogen, C₁-C₂-alkylor C₁-C₂-alkoxy;

R⁷ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;

n is 0, 1 or 2;

X is hydrogen, chlorine or bromine;

where the compounds claimed may be present both in the trans and in thecis form or as a mixture of these isomers.

Preference is given to phenyl rings and heterocycles which are eitherunsubstituted or carry one to three halogen atoms and/or one or tworadicals selected from the group consisting of: nitro, cyano, methyl,ethyl, trifluoromethyl, methoxy, ethoxy and trifluoromethoxy.

Particular preference is given to the compounds of the formula I ofTable 1, where the substituents may have the following meanings, in eachcase either alone or in combination:

R¹ is methyl, ethyl;

R² is chlorine, methyl, methoxy;

R³ is hydrogen, methyl, unsubstituted benzyl or benzyl which isfluorine-, chlorine-, methyl- or methoxy-substituted in the phenylmoiety, allyl, propyn-3-yl, methoxy, ethoxy, 2-methoxyethoxy,methylthio, methylcarbonyl, methoxycarbonyl, dimethylaminocarbonyl,cyano; preferably unsubstituted or fluorine-, chlorine-, methyl- ormethoxy-substituted phenyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl,4,5-dihydroisoxazol-3yl, isoxazol-5-yl, isoxazol-3-yl, pyrazol-1-yl,pyrazol-5-yl, oxazol-2-yl, 4,5-dihydrooxazol-2-yl, 1,3-dioxolan-2-yl,1,3-dithiolan-2-yl, thiazol-2-yl, thiazol-5-yl, thiazol-4-yl,[1,2,4]-triazol-1-yl, [1,3,4]-oxadiazol-2-yl, 2-pyridyl, 3-pyridyl,4-pyridyl, pyrimidin-2-yl, pyrimidin-4-yl, 1,3-dioxan-2-yl,1,3-dithian-2-yl;

R⁴ is methyl;

R⁷ is hydrogen;

n is 2;

X is chlorine.

The benzoylpyrazoles of the formula II in which R³ is an unsubstitutedor substituted 5- or 6-membered saturated or unsaturated heterocycle arenovel. Benzoylpyrazoles of the formula II which are particularlysuitable for use as intermediates for preparing the herbicidally activecompounds described in DE Appl. No. 19740494.4 are those where thesubstituents have the following meanings:

R¹ are C₁-C₄-alkyl or C₁-C₄-haloalkyl;

R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,halogen;

R³ is an unsubstituted or C₁-C₄-alkyl-, C₁-C₄-alkoxy-, C₁-C₄-haloalkyl-,C₁-C₄-haloalkoxy- or halogen-substituted 5- or 6-membered saturated orunsaturated heterocycle selected from the group consisting oftetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl,isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl,imidazolidinyl, 1,2,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl,1,2,4-triazolidinyl, 1,3,4-oxadiazolidinyl, 1,3,4-thiadiazolidinyl,1,3,4-triazolidinyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl,2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-dihydropyrrolyl,2,5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl,2,5-dihydroisoxazolyl, 2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl,4,5-dihydroisothiazolyl, 2,5-dihydroisothiazolyl, 2,3-dihydropyrazolyl,4,5-dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl,4,5-dihydrooxazolyl, 2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl,4,5-dihydrothiazolyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl,4,5-dihydroimidazolyl, 2,5-dihydroimidazolyl, morpholinyl, piperidinyl,tetrahydropyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl,1,3,5-tetrahydrotriazinyl, 1,2,4-tetrahydrotriazinyl,1,3-dihydrooxazinyl, 1,3-dithianyl, tetrahydropyranyl,tetrahydrothiopyranyl, 1,3-dioxolanyl,1,1-dioxo-2,3,4,5-tetrahydrothienyl, 1,3-dihydrooxazinyl, furyl,thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl,thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl,1,2,4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl,1,3,4-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl, particularpreference is given to: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl,4,5-dihydroisoxazol-3-yl, isoxazol-5-yl, isoxazol-3-yl, pyrazol-1-yl,pyrazol-5-yl, oxazol-2-yl, 4,5-dihydrooxazol-2-yl, 1,3-dioxolan-2-yl,1,3-dithiolan-2-yl, thiazol-2-yl, thiazol-5-yl, thiazol-4-yl,[1,2,4]-triazol-1-yl, [1,3,4]-oxadiazol-2-yl, 2-pyridyl, 3-pyridyl,4-pyridyl, pyrimidin-2-yl, pyrimidin-4-yl, 1,3-dioxan-2-yl,1,3-dithian-2-yl;

R⁴ is C₁-C₄-alkyl or C₁-C₄-haloalkyl;

R⁷ is hydrogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl;

n is 0, 1, 2;

x is chlorine, bromine.

Particular preference is given to the compounds II of Table 2.

PREPARATION EXAMPLES

1)cis-4-[Chloro(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)methylene]-2methyl-2,4dihydropyrazol-3-one(Tab.1 No. I.20):

5.0 g of (2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-yl)-methanone in 15 mlof toluene were mixed with 2.0 g of phosphorus oxychloride and two dropsof dimethylformamide and heated under reflux for 7 h. A further 1.0 g ofphosphorus oxychloride were added and the mixture was heated underreflux for a further 7 h. The reaction mixture was then added to 125 mlof ice-water and extracted with methyl tert-butyl ether. The crudeproduct was chromatographed over silica gel using cyclohexane/ethylacetate/methanol. Yield: 1.3 g of a colorless solid (cis isomer). ¹H NMR(CDCl₃): d=3.27 (s); 3.31 (s); 3.45 (t); 4.57 (t); 7.65 (d); 7.73 (s);8.15 (d). Additionally, the isomeric benzoylpyrazole was isolated duringthe chromatographic purification of the reaction mixture:(5-Chloro-1-methylpyrazol-4-yl)-(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)methanone(Tab. 2 No. II.17):

¹H NMR (CDCl₃): d=3.30 (s); 3.45 (t); 3.93 (s), 4.63 (t); 7.61 (d); 7.75(s); 8.17 (d).

2-cis-4-[Chloro(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)methylene]-2-ethyl-2,4-dihydropyrazol-3-one(Tab.1 No. I.119):

The compound can be prepared by the method of Example 1. Colorless solid(cis isomer); ¹H NMR (CDCl₃): d=1.28 (t); 3.27 (s) 3.46 (t); 3.72 (q),4.62 (t); 7.64 (d); 7.73 (s); 8.16 (d). Additionally, the isomericbenzoylpyrazole was isolated during the chromatographic purification ofthe reaction mixture:

(5-Chloro-1-ethylpyrazol-4-yl)-(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)methanone(Tab.2 No. II.56):

¹H NMR (CDCl₃): d=1.50 (t); 3.28 (s); 3.45 (t); 4.28 (q), 4.63 (t); 7.63(d); 7.74 (s); 8.18 (d).

3)cis-4-[Bromo(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)methylene]-2-methyl-2,4-dihydropyrazol-3-one(Tab.1 No. I.466):

2.5 g of(2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylphenyl)(5-hydroxy-1-methyl-1H-pyrazol-4-yl)-methanonein 20 ml of toluene were admixed with 1.87 g of phosphorus oxybromideand two drops of dimethylformamide and heated under reflux for 13 h. Thereaction mixture was then poured into a 50° C. sodium carbonate solutionand extracted with methyl tert-butyl ether. The crude product waschromatographed over silica gel using cyclohexane/ethylacetate/methanol. ¹H NMR (CDCl₃): d=3.25 (s); 3.31 (s); 3.43 (m); 4.59(t); 7.57 (d); 7.63 (s); 8.15 (d).

The benzylidenepyrazolones of the formula I and benzoylpyrazoles of theformula II listed in Tables 1 and 2 below can be synthesized by a methodsimilar to the procedures given in the synthesis examples above.

TABLE 1

No. R¹ R² R³ R⁴ R⁷ X n Isomer Phys. Data I.1 CH₃ Cl H CH₃ H Cl 2 cis I.2CH₃ Cl F CH₃ H Cl 2 cis I.3 CH₃ Cl Cl CH₃ H Cl 2 cis I.4 CH₃ Cl Br CH₃ HCl 2 cis I.5 CH₃ Cl CH₃ CH₃ H Cl 2 cis I.6 CH₃ Cl CF₃ CH₃ H Cl 2 cis I.7CH₃ Cl CHF₂ CH₃ H Cl 2 cis I.8 CH₃ Cl ethyl CH₃ H Cl 2 cis I.9 CH₃ Clisopropyl CH₃ H Cl 2 cis I.10 CH₃ Cl benzyl CH₃ H Cl 2 cis I.11 CH₃ Cl4-chlorophenylmethyl CH₃ H Cl 2 cis I.12 CH₃ Cl allyl CH₃ H Cl 2 cisI.13 CH₃ Cl trans-chloroallyl CH₃ H Cl 2 cis I.14 CH₃ Cl cis-chloroallylCH₃ H Cl 2 cis I.15 CH₃ Cl cis-2-chlorovinyl CH₃ H Cl 2 cis I.16 CH₃ Cltrans-2-chlorovinyl CH₃ H Cl 2 cis I.17 CH₃ Cl 2,2-dichlorovinyl CH₃ HCl 2 cis I.18 CH₃ Cl propyn-3-yl CH₃ H Cl 2 cis I.19 CH₃ Cl ethynyl CH₃H Cl 2 cis I.20 CH₃ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis seeExample 1 I.21 CH₃ Cl isoxazol-3-yl CH₃ H Cl 2 cis I.22 CH₃ Cl3-methylisoxazol-5-yl CH₃ H Cl 2 cis I.23 CH₃ Cl4-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.24 CH₃ Cl3-ethyl-4,5-dihydroisoxazol-4-yl CH₃ H Cl 2 cis I.25 CH₃ Cl3-ethyl-4,5-dihydroisoxazol-5-yl CH₃ H Cl 2 cis I.26 CH₃ Cl5-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.27 CH₃ Cl4,5-dimethyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.28 CH₃ Clthiazol-2-yl CH₃ H Cl 2 cis I.29 CH₃ Cl 5-methylthiazol-2-yl CH₃ H Cl 2cis I.30 CH₃ Cl thiazol-4-yl CH₃ H Cl 2 cis I.31 CH₃ Cl thiazol-5-yl CH₃H Cl 2 cis I.32 CH₃ Cl oxazol-2-yl CH₃ H Cl 2 cis I.33 CH₃ Cl4,5-dihydrooxazol-2-yl CH₃ H Cl 2 cis I.34 CH₃ Cl pyrrol-1-yl CH₃ H Cl 2cis I.35 CH₃ Cl pyrazol-1-yl CH₃ H Cl 2 cis I.36 CH₃ Cl1-methylpyrazol-5-yl CH₃ H Cl 2 cis I.37 CH₃ Cl 1-methylpyrazol-3-yl CH₃H Cl 2 cis I.38 CH₃ Cl 1-methoxypyrazol-5-yl CH₃ H Cl 2 cis I.39 CH₃ Cl1-methoxypyrazol-3-yl CH₃ H Cl 2 cis I.40 CH₃ Cl 1-methylimidazol-2-ylCH₃ H Cl 2 cis I.41 CH₃ Cl imidazol-1-yl CH₃ H Cl 2 cis I.42 CH₃ Cl[1,2,4]-triazol-1-yl CH₃ H Cl 2 cis I.43 CH₃ Cl1-methyl-[1,2,4]-triazol-3-yl CH₃ H Cl 2 cis I.44 CH₃ Cl 2-thienyl CH₃ HCl 2 cis I.45 CH₃ Cl 3-thienyl CH₃ H Cl 2 cis I.46 CH₃ Cltetrahydrothiopyran-3-yl CH₃ H Cl 2 cis I.47 CH₃ Cltetrahydrothiopyran-4-yl CH₃ H Cl 2 cis I.48 CH₃ Cl [1,3]dithiolan-2-ylCH₃ H Cl 2 cis I.49 CH₃ Cl 2-furyl CH₃ H Cl 2 cis I.50 CH₃ Cl 3-furylCH₃ H Cl 2 cis I.51 CH₃ Cl tetrahydrofuran-2-yl CH₃ H Cl 2 cis I.52 CH₃Cl tetrahydrofuran-3-yl CH₃ H Cl 2 cis I.53 CH₃ Cl [1,3]dioxolan-2-ylCH₃ H Cl 2 cis I.54 CH₃ Cl tetrahydropyran-3-yl CH₃ H Cl 2 cis I.55 CH₃Cl tetrahydropyran-4-yl CH₃ H Cl 2 cis I.56 CH₃ Cl [1,3]dioxan-2-yl CH₃H Cl 2 cis I.57 CH₃ Cl [1,3,4]-oxadiazol-2-yl CH₃ H Cl 2 cis I.58 CH₃ Clpiperidin-1-yl CH₃ H Cl 2 cis I.59 CH₃ Cl 2-pyridyl CH₃ H Cl 2 cis I.60CH₃ Cl 6-methoxy-2-pyridyl CH₃ H Cl 2 cis I.61 CH₃ Cl5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.62 CH₃ Cl2-chloro-5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.63 CH₃ Cl3-pyridyl CH₃ H Cl 2 cis I.64 CH₃ Cl 4-pyridyl CH₃ H Cl 2 cis I.65 CH₃Cl morpholin-4-yl CH₃ H Cl 2 cis I.66 CH₃ Cl pyrimidin-2-yl CH₃ H Cl 2cis I.67 CH₃ Cl pyrimidin-4-yl CH₃ H Cl 2 cis I.68 CH₃ Cl pyrazin-2-ylCH₃ H Cl 2 cis I.69 CH₃ Cl pyridazin-3-yl CH₃ H Cl 2 cis I.70 CH₃ Clpyridazin-4-yl CH₃ H Cl 2 cis I.71 CH₃ Cl 6-methylpyridazin-3-yl CH₃ HCl 2 cis I.72 CH₃ Cl 6-methoxypyridazin-3-yl CH₃ H Cl 2 cis I.73 CH₃ Cl[1,3,5]-triazin-2-yl CH₃ H Cl 2 cis I.74 CH₃ Cl [1,2,4]-triazin-3-yl CH₃H Cl 2 cis I.75 CH₃ Cl phenyl CH₃ H Cl 2 cis I.76 CH₃ Cl 2-fluorophenylCH₃ H Cl 2 cis I.77 CH₃ Cl 3-trifluoromethylphenyl CH₃ H Cl 2 cis I.78CH₃ Cl 2-methylphenyl CH₃ H Cl 2 cis I.79 CH₃ Cl 3-methylphenyl CH₃ H Cl2 cis I.80 CH₃ Cl 4-methylphenyl CH₃ H Cl 2 cis I.81 CH₃ Cl4-chlorophenyl CH₃ H Cl 2 cis I.82 CH₃ Cl 2-chlorophenyl CH₃ H Cl 2 cisI.83 CH₃ Cl 3-chlorophenyl CH₃ H Cl 2 cis I.84 CH₃ Cl 4-methoxyphenylCH₃ H Cl 2 cis - I.85 CH₃ Cl methylthio CH₃ H Cl 2 cis I.86 CH₃ Clmethoxy CH₃ H Cl 2 cis I.87 CH₃ Cl ethoxy CH₃ H Cl 2 cis I.88 CH₃ Cl2-methoxyethoxy CH₃ H Cl 2 cis I.89 CH₃ Cl formyl CH₃ H Cl 2 cis I.90CH₃ Cl acetylamino CH₃ H Cl 2 cis I.91 CH₃ Cl methylcarbonyl CH₃ H Cl 2cis I.92 CH₃ Cl methoxycarbonyl CH₃ H Cl 2 cis I.93 CH₃ Cldimethylaminocarbonyl CH₃ H Cl 2 cis I.94 CH₃ Cl methoxyiminomethyl CH₃H Cl 2 cis I.95 CH₃ Cl ethoxyiminomethyl CH₃ H Cl 2 cis I.96 CH₃ Cl1-ethoxyiminoethyl CH₃ H Cl 2 cis I.97 CH₃ Cl 1-methoxyiminoethyl CH₃ HCl 2 cis I.98 CH₃ Cl 1-ethoxyiminopropyl CH₃ H Cl 2 cis I.99 CH₃ Cl1-methoxyiminopropy1 CH₃ H Cl 2 cis I.100 CH₃ Cl cyano CH₃ H Cl 2 cisI.101 C₂H₅ Cl H CH₃ H Cl 2 cis I.102 C₂H₅ Cl Cl CH₃ H Cl 2 cis I.103C₂H₅ Cl Br CH₃ H Cl 2 cis I.104 C₂H₅ Cl CH₃ CH₃ H Cl 2 cis I.105 C₂H₅ ClCF₃ CH₃ H Cl 2 cis I.106 C₂H₅ Cl CHF₂ CH₃ H Cl 2 cis I.107 C₂H₅ Cl ethylCH₃ H Cl 2 cis I.108 C₂H₅ Cl isopropyl CH₃ H Cl 2 cis I.109 C₂H₅ Clbenzyl CH₃ H Cl 2 cis I.110 C₂H₅ Cl 4-chlorophenylmethyl CH₃ H Cl 2 cisI.111 C₂H₅ Cl allyl CH₃ H Cl 2 cis I.112 C₂H₅ Cl trans-chloroallyl CH₃ HCl 2 cis I.113 C₂H₅ Cl cis-chloroallyl CH₃ H Cl 2 cis I.114 C₂H₅ Clcis-2-chlorovinyl CH₃ H Cl 2 cis I.115 C₂H₅ Cl trans-2-chlorovinyl CH₃ HCl 2 cis I.116 C₂H₅ Cl 2,2-dichiorovinyl CH₃ H Cl 2 cis I.117 C₂H₅ Clpropyn-3-yl CH₃ H Cl 2 cis I.118 C₂H₅ Cl ethynyl CH₃ H Cl 2 cis I.119C₂H₅ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis see Example 2 I.120 C₂H₅Cl isoxazol-3-yl CH₃ H Cl 2 cis I.121 C₂H₅ Cl 3-methylisoxazol-5-yl CH₃H Cl 2 cis I.122 C₂H₅ Cl 4-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2cis I.123 C₂H₅ Cl 3-ethyl-4,5-dihydroisoxazol-4-yl CH₃ H Cl 2 cis I.124C₂H₅ Cl 3-ethyl-4,5-dihydroisoxazol-5-yl CH₃ H Cl 2 cis I.125 C₂H₅ Cl5-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.126 C₂H₅ Cl4,5-dimethyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.127 C₂H₅ Clthiazol-2-yl CH₃ H Cl 2 cis I.128 C₂H₅ Cl 5-methylthiazol-2-yl CH₃ H Cl2 cis I.129 C₂H₅ Cl thiazol-4-yl CH₃ H Cl 2 cis I.130 C₂H₅ Clthiazol-5-yl CH₃ H Cl 2 cis I.131 C₂H₅ Cl oxazol-2-yl CH₃ H Cl 2 cisI.132 C₂H₅ Cl 4,5-dihydrooxazol-2-yl CH₃ H Cl 2 cis I.133 C₂H₅ Clpyrrol-1-yl CH₃ H Cl 2 cis I.134 C₂H₅ Cl pyrazol-1-yl CH₃ H Cl 2 cisI.135 C₂H₅ Cl 1-methylpyrazol-5-yl CH₃ H Cl 2 cis I.136 C₂H₅ Cl1-methylpyrazol-3-yl CH₃ H Cl 2 cis I.137 C₂H₅ Cl 1-methoxypyrazol-5-ylCH₃ H Cl 2 cis I.138 C₂H₅ Cl 1-methoxypyrazol-3-yl CH₃ H Cl 2 cis I.139C₂H₅ Cl 1-methylimidazol-2-yl CH₃ H Cl 2 cis I.140 C₂H₅ Cl imidazol-1-ylCH₃ H Cl 2 cis I.141 C₂H₅ Cl [1,2,4]-triazol-1-yl CH₃ H Cl 2 cis I.142C₂H₅ Cl 1-methyl-[1,2,4]-triazol-3-yl CH₃ H Cl 2 cis I.143 C₂H₅ Cl2-thienyl CH₃ H Cl 2 cis I.144 C₂H₅ Cl 3-thienyl CH₃ H Cl 2 cis I.145C₂H₅ Cl tetrahydrothiopyran-3-yl CH₃ H Cl 2 cis I.146 C₂H₅ Cltetrahydrothiopyran-4-yl CH₃ H Cl 2 cis I.147 C₂H₅ Cl[1,3]dithiolan-2-yl CH₃ H Cl 2 cis I.148 C₂H₅ Cl 2-furyl CH₃ H Cl 2 cisI.149 C₂H₅ Cl 3-furyl CH₃ H Cl 2 cis I.150 C₂H₅ Cl tetrahydrofuran-2-ylCH₃ H Cl 2 cis I.151 C₂H₅ Cl tetrahydrofuran-3-yl CH₃ H Cl 2 cis I.152C₂H₅ Cl [1,3]dioxolan-2-yl CH₃ H Cl 2 cis I.153 C₂H₅ Cltetrahydropyran-3-yl CH₃ H Cl 2 cis I.154 C₂H₅ Cl tetrahydropyran-4-ylCH₃ H Cl 2 cis I.155 C₂H₅ Cl [1,3]dioxan-2-yl CH₃ H Cl 2 cis I.156 C₂H₅Cl [1,3,4]-oxadiazol-2-yl CH₃ H Cl 2 cis I.157 C₂H₅ Cl piperidin-1-ylCH₃ H Cl 2 cis I.158 C₂H₅ Cl 2-pyridyl CH₃ H Cl 2 cis I.159 C₂H₅ Cl6-methoxy-2-pyridyl CH₃ H Cl 2 cis I.160 C₂H₅ Cl5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.161 C₂H₅ Cl2-chloro-5-trifluoromethyhl-2-pyridyl CH₃ H Cl 2 cis I.162 C₂H₅ Cl3-pyridyl CH₃ H Cl 2 cis I.163 C₂H₅ Cl 4-pyridyl CH₃ H Cl 2 cis I.164C₂H₅ Cl morpholin-4-yl CH₃ H Cl 2 cis I.165 C₂H₅ Cl pyrimidin-2-yl CH₃ HCl 2 cis I.166 C₂H₅ Cl pyrimidin-4-yl CH₃ H Cl 2 cis I.167 C₂H₅ Clpyrazin-2-yl CH₃ H Cl 2 cis I.168 C₂H₅ Cl pyridazin-3-yl CH₃ H Cl 2 cisI.169 C₂H₅ Cl pyridazin-4-yl CH₃ H Cl 2 cis I.170 C₂H₅ Cl6-methylpyridazin-3-yl CH₃ H Cl 2 cis I.171 C₂H₅ Cl6-methoxypyridazin-3-yl CH₃ H Cl 2 cis I.172 C₂H₅ Cl[1,3,5]-triazin-2-yl CH₃ H Cl 2 cis I.173 C₂H₅ Cl [1,2,4]-triazin-3-ylCH₃ H Cl 2 cis I.174 C₂H₅ Cl phenyl CH₃ H Cl 2 cis I.175 C₂H₅ Cl2-fluorophenyl CH₃ H Cl 2 cis I.176 C₂H₅ Cl 3-trifluoromethylphenyl CH₃H Cl 2 cis I.177 C₂H₅ Cl 2-methylphenyl CH₃ H Cl 2 cis I.178 C₂H₅ Cl3-methylphenyl CH₃ H Cl 2 cis I.179 C₂H₅ Cl 4-methylphenyl CH₃ H Cl 2cis I.180 C₂H₅ Cl 4-chlorophenyl CH₃ H Cl 2 cis I.181 C₂H₅ Cl2-chlorophenyl CH₃ H Cl 2 cis I.182 C₂H₅ Cl 3-chlorophenyl CH₃ H Cl 2cis I.183 C₂H₅ Cl 4-methoxyphenyl CH₃ H Cl 2 cis I.184 C₂H₅ Clmethylthio CH₃ H Cl 2 cis I.185 C₂H₅ Cl methoxy CH₃ H Cl 2 cis I.186C₂H₅ Cl ethoxy CH₃ H Cl 2 cis I.187 C₂H₅ Cl 2-methoxyethoxy CH₃ H Cl 2cis I.188 C₂H₅ Cl formyl CH₃ H Cl 2 cis I.189 C₂H₅ Cl acetylamino CH₃ HCl 2 cis I.190 C₂H₅ Cl methylcarbonyl CH₃ H Cl 2 cis I.191 C₂H₅ Clmethoxycarbonyl CH₃ H Cl 2 cis I.192 C₂H₅ Cl dimethylaminocarbonyl CH₃ HCl 2 cis I.193 C₂H₅ Cl methoxyiminomethyl CH₃ H Cl 2 cis I.194 C₂H₅ Clethoxyiminomethyl CH₃ H Cl 2 cis I.195 C₂H₅ Cl 1-ethoxyiminoethyl CH₃ HCl 2 cis I.196 C₂H₅ Cl 1-methoxyiminopropyl CH₃ H Cl 2 cis I.197 C₂H₅ Cl1-ethoxyiminopropyl CH₃ H Cl 2 cis I.198 C₂H₅ Cl 1-methyliminopropyl CH₃H Cl 2 cis I.199 C₂H₅ Cl cyano CH₃ H Cl 2 cis I.200 CH₃ CH₃ H CH₃ H Cl 2cis I.201 CH₃ CH₃ F CH₃ H Cl 2 cis I.202 CH₃ CH₃ Cl CH₃ H Cl 2 cis I.203CH₃ CH₃ Br CH₃ H Cl 2 cis I.204 CH₃ CH₃ CH₃ CH₃ H Cl 2 cis I.205 CH₃ CH₃CF₃ CH₃ H Cl 2 cis I.206 CH₃ CH₃ CHF₂ CH₃ H Cl 2 cis I.207 CH₃ CH₃ ethylCH₃ H Cl 2 cis I.208 CH₃ CH₃ isopropyl CH₃ H Cl 2 cis I.209 CH₃ CH₃benzyl CH₃ H Cl 2 cis I.210 CH₃ CH₃ 4-chlorophenylmethyl CH₃ H Cl 2 cisI.211 CH₃ CH₃ allyl CH₃ H Cl 2 cis I.212 CH₃ CH₃ trans-chloroallyl CH₃ HCl 2 cis I.213 CH₃ CH₃ cis-chloroallyl CH₃ H Cl 2 cis I.214 CH₃ CH₃cis-2-chlorovinyl CH₃ H Cl 2 cis I.215 CH₃ CH₃ trans-2-chlorovinyl CH₃ HCl 2 cis I.216 CH₃ CH₃ 2,2-dichlorovinyl CH₃ H Cl 2 cis I.217 CH₃ CH₃propyn-3-yl CH₃ H Cl 2 cis I.218 CH₃ CH₃ ethynyl CH₃ H Cl 2 cis I.219CH₃ CH₃ 4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.220 CH₃ CH₃isoxazol-3-yl CH₃ H Cl 2 cis I.221 CH₃ CH₃ 3-methylisoxazol-5-yl CH₃ HCl 2 cis I.222 CH₃ CH₃ 4-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cisI.223 CH₃ CH₃ 3-ethyl-4,5-dihydroisoxazol-4-yl CH₃ H Cl 2 cis I.224 CH₃CH₃ 3-ethyl-4,5-dihydroisoxazol-5-yl CH₃ H Cl 2 cis I.225 CH₃ CH₃5-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.226 CH₃ CH₃4,5-dimethyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.227 CH₃ CH₃thiazol-2-yl CH₃ H Cl 2 cis I.228 CH₃ CH₃ 5-methylthiazol-2-yl CH₃ H Cl2 cis I.229 CH₃ CH₃ thiazol-4-yl CH₃ H Cl 2 cis I.230 CH₃ CH₃thiazol-5-yl CH₃ H Cl 2 cis I.231 CH₃ CH₃ oxazol-2-yl CH₃ H Cl 2 cisI.232 CH₃ CH₃ 4,5-dihydrooxazol-2-yl CH₃ H Cl 2 cis I.233 CH₃ CH₃pyrrol-1-yl CH₃ H Cl 2 cis I.234 CH₃ CH₃ pyrazol-1-yl CH₃ H Cl 2 cisI.235 CH₃ CH₃ 1-methylpyrazol-5-yl CH₃ H Cl 2 cis I.236 CH₃ CH₃1-methylpyrazol-3-yl CH₃ H Cl 2 cis I.237 CH₃ CH₃ 1-methoxypyrazol-5-ylCH₃ H Cl 2 cis I.238 CH₃ CH₃ 1-methoxypyrazol-3-yl CH₃ H Cl 2 cis I.239CH₃ CH₃ 1-methylimidazol-2-yl CH₃ H Cl 2 cis I.240 CH₃ CH₃ imidazol-1-ylCH₃ H Cl 2 cis I.241 CH₃ CH₃ [1,2,4]-triazol-1-yl CH₃ H Cl 2 cis I.242CH₃ CH₃ 1-methyl-[1,2,4]-triazol-3-yl CH₃ H Cl 2 cis I.243 CH₃ CH₃2-thienyl CH₃ H Cl 2 cis I.244 CH₃ CH₃ 3-thienyl CH₃ H Cl 2 cis I.245CH₃ CH₃ tetrahydrothiopyran-3-yl CH₃ H Cl 2 cis I.246 CH₃ CH₃tetrahydrothiopyran-4-yl CH₃ H Cl 2 cis I.247 CH₃ CH₃[1,3]dithiolan-2-yl CH₃ H Cl 2 cis I.248 CH₃ CH₃ 2-furyl CH₃ H Cl 2 cisI.249 CH₃ CH₃ 3-furyl CH₃ H Cl 2 cis I.250 CH₃ CH₃ tetrahydrofuran-2-ylCH₃ H Cl 2 cis I.251 CH₃ CH₃ tetrahydrofuran-3-yl CH₃ H Cl 2 cis I.252CH₃ CH₃ [1,3]dioxolan-2-yl CH₃ H Cl 2 cis I.253 CH₃ CH₃tetrahydropyran-3-yl CH₃ H Cl 2 cis I.254 CH₃ CH₃ tetrahydropyran-4-ylCH₃ H Cl 2 cis I.255 CH₃ CH₃ [1,3]dioxan-2-yl CH₃ H Cl 2 cis I.256 CH₃CH₃ [1,3,4]-oxadiazol-2-yl CH₃ H Cl 2 cis I.257 CH₃ CH₃ piperidin-1-ylCH₃ H Cl 2 cis I.258 CH₃ CH₃ 2-pyridyl CH₃ H Cl 2 cis I.259 CH₃ CH₃6-methoxy-2-pyridyl CH₃ H Cl 2 cis I.260 CH₃ CH₃5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.261 CH₃ CH₃2-chloro-5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.262 CH₃ CH₃3-pyridyl CH₃ H Cl 2 cis I.263 CH₃ CH₃ 4-pyridyl CH₃ H Cl 2 cis I.264CH₃ CH₃ morpholin-4-yl CH₃ H Cl 2 cis I.265 CH₃ CH₃ pyrimidin-2-yl CH₃ HCl 2 cis I.266 CH₃ CH₃ pyrimidin-4-yl CH₃ H Cl 2 cis I.267 CH₃ CH₃pyrazin-2-yl CH₃ H Cl 2 cis I.268 CH₃ CH₃ pyridazin-3-yl CH₃ H Cl 2 cisI.269 CH₃ CH₃ pyridazin-4-yl CH₃ H Cl 2 cis I.270 CH₃ CH₃6-methylpyridazin-3-yl CH₃ H Cl 2 cis I.271 CH₃ CH₃6-methoxypyridazin-3-yl CH₃ H Cl 2 cis I.272 CH₃ CH₃[1,3,5]-triazin-2-yl CH₃ H Cl 2 cis I.273 CH₃ CH₃ [1,2,4]-triazin-3-ylCH₃ H Cl 2 cis I.274 CH₃ CH₃ phenyl CH₃ H Cl 2 cis I.275 CH₃ CH₃2-fluorophenyl CH₃ H Cl 2 cis I.276 CH₃ CH₃ 3-trifluoromethylphenyl CH₃H Cl 2 cis I.277 CH₃ CH₃ 2-methylphenyl CH₃ H Cl 2 cis I.278 CH₃ CH₃3-methylphenyl CH₃ H Cl 2 cis I.279 CH₃ CH₃ 4-methylphenyl CH₃ H Cl 2cis I.280 CH₃ CH₃ 4-chlorophenyl CH₃ H Cl 2 cis I.281 CH₃ CH₃2-chlorophenyl CH₃ H Cl 2 cis I.282 CH₃ CH₃ 3-chlorophenyl CH₃ H Cl 2cis I.283 CH₃ CH₃ 4-methoxyphenyl CH₃ H Cl 2 cis - I.284 CH₃ CH₃methylthio CH₃ H Cl 2 cis I.285 CH₃ CH₃ methoxy CH₃ H Cl 2 cis I.286 CH₃CH₃ ethoxy CH₃ H Cl 2 cis I.287 CH₃ CH₃ 2-methoxyethoxy CH₃ H Cl 2 cisI.288 CH₃ CH₃ formyl CH₃ H Cl 2 cis I.289 CH₃ CH₃ acetylamino CH₃ H Cl 2cis I.290 CH₃ CH₃ methylcarbonyl CH₃ H Cl 2 cis I.291 CH₃ CH₃methoxycarbonyl CH₃ H Cl 2 cis I.292 CH₃ CH₃ dimethylaminocarbonyl CH₃ HCl 2 cis I.293 CH₃ CH₃ methoxyiminomethyl CH₃ H Cl 2 cis I.294 CH₃ CH₃ethoxyiminomethyl CH₃ H Cl 2 cis I.295 CH₃ CH₃ 1-ethoxyiminoethyl CH₃ HCl 2 cis I.296 CH₃ CH₃ 1-methoxyiminoethyl CH₃ H Cl 2 cis I.297 CH₃ CH₃1-ethoxyiminopropyl CH₃ H Cl 2 cis I.298 CH₃ CH₃ 1-methoxyiminopropy1CH₃ H Cl 2 cis I.299 CH₃ CH₃ cyano CH₃ H Cl 2 cis I.300 C₂H₅ CH₃ H CH₃ HCl 2 cis I.301 C₂H₅ CH₃ F CH₃ H Cl 2 cis I.302 C₂H₅ CH₃ Cl CH₃ H Cl 2cis I.303 C₂H₅ CH₃ Br CH₃ H Cl 2 cis I.304 C₂H₅ CH₃ CH₃ CH₃ H Cl 2 cisI.305 C₂H₅ CH₃ CF₃ CH₃ H Cl 2 cis I.306 C₂H₅ CH₃ CHF₂ CH₃ H Cl 2 cisI.307 C₂H₅ CH₃ ethyl CH₃ H Cl 2 cis I.308 C₂H₅ CH₃ isopropyl CH₃ H Cl 2cis I.309 C₂H₅ CH₃ benzyl CH₃ H Cl 2 cis I.310 C₂H₅ CH₃4-chlorophenylmethyl CH₃ H Cl 2 cis I.311 C₂H₅ CH₃ allyl CH₃ H Cl 2 cisI.312 C₂H₅ CH₃ trans-chloroallyl CH₃ H Cl 2 cis I.313 C₂H₅ CH₃cis-chloroallyl CH₃ H Cl 2 cis I.314 C₂H₅ CH₃ cis-2-chlorovinyl CH₃ H Cl2 cis I.315 C₂H₅ CH₃ trans-2-chlorovinyl CH₃ H Cl 2 cis I.316 C₂H₅ CH₃2,2-dichlorovinyl CH₃ H Cl 2 cis I.317 C₂H₅ CH₃ propyn-3-yl CH₃ H Cl 2cis I.318 C₂H₅ CH₃ ethynyl CH₃ H Cl 2 cis I.319 C₂H₅ CH₃4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.320 C₂H₅ CH₃ isoxazol-3-yl CH₃H Cl 2 cis I.321 C₂H₅ CH₃ 3-methylisoxazol-5-yl CH₃ H Cl 2 cis I.322C₂H₅ CH₃ 4-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.323 C₂H₅ CH₃3-ethyl-4,5-dihydroisoxazol-4-yl CH₃ H Cl 2 cis I.324 C₂H₅ CH₃3-ethyl-4,5-dihydroisoxazol-5-yl CH₃ H Cl 2 cis I.325 C₂H₅ CH₃5-methyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.326 C₂H₅ CH₃4,5-dimethyl-4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 cis I.327 C₂H₅ CH₃thiazol-2-yl CH₃ H Cl 2 cis I.328 C₂H₅ CH₃ 5-methylthiazol-2-yl CH₃ H Cl2 cis I.329 C₂H₅ CH₃ thiazol-4-yl CH₃ H Cl 2 cis I.330 C₂H₅ CH₃thiazol-5-yl CH₃ H Cl 2 cis I.331 C₂H₅ CH₃ oxazol-2-yl CH₃ H Cl 2 cisI.332 C₂H₅ CH₃ 4,5-dihydrooxazol-2-yl CH₃ H Cl 2 cis I.333 C₂H₅ CH₃pyrrol-1-yl CH₃ H Cl 2 cis I.334 C₂H₅ CH₃ pyrazol-1-yl CH₃ H Cl 2 cisI.335 C₂H₅ CH₃ 1-methylpyrazol-5-yl CH₃ H Cl 2 cis I.336 C₂H₅ CH₃1-methylpyrazol-3-yl CH₃ H Cl 2 cis I.337 C₂H₅ CH₃ 1-methoxypyrazol-5-ylCH₃ H Cl 2 cis I.338 C₂H₅ CH₃ 1-methoxypyrazol-3-yl CH₃ H Cl 2 cis I.339C₂H₅ CH₃ 1-methylimidazol-2-yl CH₃ H Cl 2 cis I.340 C₂H₅ CH₃imidazol-1-yl CH₃ H Cl 2 cis I.341 C₂H₅ CH₃ [1,2,4]-triazol-1-yl CH₃ HCl 2 cis I.342 C₂H₅ CH₃ 1-methyl-[1,2,4]-triazol-3-yl CH₃ H Cl 2 cisI.343 C₂H₅ CH₃ 2-thienyl CH₃ H Cl 2 cis I.344 C₂H₅ CH₃ 3-thienyl CH₃ HCl 2 cis I.345 C₂H₅ CH₃ tetrahydrothiopyran-3-yl CH₃ H Cl 2 cis I.346C₂H₅ CH₃ tetrahydrothiopyran-4-yl CH₃ H Cl 2 cis I.347 C₂H₅ CH₃[1,3]dithiolan-2-yl CH₃ H Cl 2 cis I.348 C₂H₅ CH₃ 2-furyl CH₃ H Cl 2 cisI.349 C₂H₅ CH₃ 3-furyl CH₃ H Cl 2 cis I.350 C₂H₅ CH₃tetrahydrofuran-2-yl CH₃ H Cl 2 cis I.351 C₂H₅ CH₃ tetrahydrofuran-3-ylCH₃ H Cl 2 cis I.352 C₂H₅ CH₃ [1,3]dioxolan-2-yl CH₃ H Cl 2 cis I.353C₂H₅ CH₃ tetrahydropyran-3-yl CH₃ H Cl 2 cis I.354 C₂H₅ CH₃tetrahydropyran-4-yl CH₃ H Cl 2 cis I.355 C₂H₅ CH₃ [1,3]dioxan-2-yl CH₃H Cl 2 cis I.356 C₂H₅ CH₃ [1,3,4]-oxadiazol-2-yl CH₃ H Cl 2 cis I.357C₂H₅ CH₃ piperidin-1-yl CH₃ H Cl 2 cis I.358 C₂H₅ CH₃ 2-pyridyl CH₃ H Cl2 cis I.359 C₂H₅ CH₃ 6-methoxy-2-pyridyl CH₃ H Cl 2 cis I.360 C₂H₅ CH₃5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.361 C₂H₅ CH₃2-chloro-5-trifluoromethyl-2-pyridyl CH₃ H Cl 2 cis I.362 C₂H₅ CH₃3-pyridyl CH₃ H Cl 2 cis I.363 C₂H₅ CH₃ 4-pyridyl CH₃ H Cl 2 cis I.364C₂H₅ CH₃ morpholin-4-yl CH₃ H Cl 2 cis I.365 C₂H₅ CH₃ pyrimidin-2-yl CH₃H Cl 2 cis I.366 C₂H₅ CH₃ pyrimidin-4-yl CH₃ H Cl 2 cis I.367 C₂H₅ CH₃pyrazin-2-yl CH₃ H Cl 2 cis I.368 C₂H₅ CH₃ pyridazin-3-yl CH₃ H Cl 2 cisI.369 C₂H₅ CH₃ pyridazin-4-yl CH₃ H Cl 2 cis I.370 C₂H₅ CH₃6-methylpyridazin-3-yl CH₃ H Cl 2 cis I.371 C₂H₅ CH₃6-methoxypyridazin-3-yl CH₃ H Cl 2 cis I.372 C₂H₅ CH₃[1,3,5]-triazin-2-yl CH₃ H Cl 2 cis I.373 C₂H₅ CH₃ [1,2,4]-triazin-3-ylCH₃ H Cl 2 cis I.374 C₂H₅ CH₃ phenyl CH₃ H Cl 2 cis I.375 C₂H₅ CH₃2-fluorophenyl CH₃ H Cl 2 cis I.376 C₂H₅ CH₃ 3-trifluoromethylphenyl CH₃H Cl 2 cis I.377 C₂H₅ CH₃ 2-methylphenyl CH₃ H Cl 2 cis I.378 C₂H₅ CH₃3-methylphenyl CH₃ H Cl 2 cis I.379 C₂H₅ CH₃ 4-methylphenyl CH₃ H Cl 2cis I.380 C₂H₅ CH₃ 4-chlorophenyl CH₃ H Cl 2 cis I.381 C₂H₅ CH₃2-chlorophenyl CH₃ H Cl 2 cis I.382 C₂H₅ CH₃ 3-chlorophenyl CH₃ H Cl 2cis I.383 C₂H₅ CH₃ 4-methoxyphenyl CH₃ H Cl 2 cis - I.384 C₂H₅ CH₃methylthio CH₃ H Cl 2 cis I.385 C₂H₅ CH₃ methoxy CH₃ H Cl 2 cis I.386C₂H₅ CH₃ ethoxy CH₃ H Cl 2 cis I.387 C₂H₅ CH₃ 2-methoxyethoxy CH₃ H Cl 2cis I.388 C₂H₅ CH₃ formyl CH₃ H Cl 2 cis I.389 C₂H₅ CH₃ acetylamino CH₃H Cl 2 cis I.390 C₂H₅ CH₃ methylcarbonyl CH₃ H Cl 2 cis I.391 C₂H₅ CH₃methoxycarbonyl CH₃ H Cl 2 cis I.392 C₂H₅ CH₃ dimethylaminocarbonyl CH₃H Cl 2 cis I.393 C₂H₅ CH₃ methoxyiminomethyl CH₃ H Cl 2 cis I.394 C₂H₅CH₃ ethoxyiminomethyl CH₃ H Cl 2 cis I.395 C₂H₅ CH₃ 1-ethoxyiminoethylCH₃ H Cl 2 cis I.396 C₂H₅ CH₃ 1-methoxyiminoethyl CH₃ H Cl 2 cis I.397C₂H₅ CH₃ 1-ethoxyiminopropyl CH₃ H Cl 2 cis I.398 C₂H₅ CH₃1-methoxyiminopropy1 CH₃ H Cl 2 cis I.399 C₂H₅ CH₃ cyano CH₃ H Cl 2 cisI.400 CH₃ Cl H CF₃ H Cl 2 cis I.401 CH₃ Cl F CF₃ H Cl 2 cis I.402 CH₃ ClCl CF₃ H Cl 2 cis I.403 CH₃ Cl Br CF₃ H Cl 2 cis I.404 CH₃ Cl CH₃ CF₃ HCl 2 cis I.405 CH₃ Cl CF₃ CF₃ H Cl 2 cis I.406 CH₃ Cl ethyl CF₃ H Cl 2cis I.407 CH₃ Cl trans-chloroallyl CF₃ H Cl 2 cis I.408 CH₃ Cl2,2-dichlorovinyl CF₃ H Cl 2 cis I.409 CH₃ Cl 4,5-dihydroisoxazol-3-ylCF₃ H Cl 2 cis I.410 CH₃ Cl isoxazol-3-yl CF₃ H Cl 2 cis I.411 CH₃ Cl3-methylisoxazol-5-yl CF₃ H Cl 2 cis I.412 CH₃ Cl4-methyl-4,5-dihydroisoxazol-3-yl CF₃ H Cl 2 cis I.413 CH₃ Cl5-methyl-4,5-dihydoisoxazol-3-yl CF₃ H Cl 2 cis I.414 CH₃ Clthiazol-2-yl CF₃ H Cl 2 cis I.415 CH₃ Cl oxazol-2-yl CF₃ H Cl 2 cisI.416 CH₃ Cl 4,5-dihydrooxazol-2-yl CF₃ H Cl 2 cis I.417 CH₃ Cl1-methylpyrazol-3-yl CF₃ H Cl 2 cis I.418 CH₃ Cl 2-thienyl CF₃ H Cl 2cis I.419 CH₃ Cl 3-thienyl CF₃ H Cl 2 cis I.420 CH₃ Cl[1,3]dioxolan-2-yl CF₃ H Cl 2 cis I.421 CH₃ Cl 2-pyridyl CF₃ H Cl 2 cisI.422 CH₃ Cl 3-pyridyl CF₃ H Cl 2 cis I.423 CH₃ Cl 4-pyridyl CF₃ H Cl 2cis I.424 CH₃ Cl pyrimidin-2-yl CF₃ H Cl 2 cis I.425 CH₃ Clpyrimidin-4-yl CF₃ H Cl 2 cis I.426 CH₃ Cl pyrazin-2-yl CF₃ H Cl 2 cisI.427 CH₃ Cl pyridazin-3-yl CF₃ H Cl 2 cis I.428 CH₃ Cl phenyl CF₃ H Cl2 cis I.429 CH₃ Cl 2-fluorophenyl CF₃ H Cl 2 cis I.430 CH₃ Cl3-trifluoromethylphenyl CF₃ H Cl 2 cis I.431 CH₃ Cl 4-methylphenyl CF₃ HCl 2 cis I.432 CH₃ Cl 4-chlorophenyl CF₃ H Cl 2 cis I.433 CH₃ Cl4-methoxyphenyl CF₃ H Cl 2 cis I.434 CH₃ Cl methoxy CF₃ H Cl 2 cis I.435CH₃ Cl dimethylaminocarbonyl CF₃ H Cl 2 cis I.436 CH₃ Clmethoxyiminomethyl CF₃ H Cl 2 cis I.437 CH₃ Cl H CH₃ H Cl 1 cis I.438CH₃ Cl Cl CH₃ H Cl 1 cis I.439 CH₃ Cl CH₃ CH₃ H Cl 1 cis I.440 CH₃ Cl4,5-dihydroisoxazol-3-yl CH₃ H Cl 1 cis I.441 CH₃ Cl isoxazol-3-yl CH₃ HCl 1 cis I.442 CH₃ Cl 3-methylisoxazol-5-yl CH₃ H Cl 1 cis I.443 CH₃ Clthiazol-2-yl CH₃ H Cl 1 cis I.444 CH₃ Cl oxazol-2-yl CH₃ H Cl 1 cisI.445 CH₃ Cl 2-pyridyl CH₃ H Cl 1 cis I.446 CH₃ Cl pyrimidin-2-yl CH₃ HCl 1 cis I.447 CH₃ Cl pyrazin-2-yl CH₃ H Cl 1 cis I.448 CH₃ Cl phenylCH₃ H Cl 1 cis I.449 CH₃ Cl methoxy CH₃ H Cl 1 cis I.450 CH₃ Cl H CH₃ HCl 0 cis I.451 CH₃ Cl Cl CH₃ H Cl 0 cis I.452 CH₃ Cl CH₃ CH₃ H Cl 0 cisI.453 CH₃ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Cl 0 cis I.454 CH₃ Clisoxazol-3-yl CH₃ H Cl 0 cis I.455 CH₃ Cl 3-methylisoxazol-5-yl CH₃ H Cl0 cis I.456 CH₃ Cl thiazol-2-yl CH₃ H Cl 0 cis I.457 CH₃ Cl oxazol-2-ylCH₃ H Cl 0 cis I.458 CH₃ Cl 2-pyridyl CH₃ H Cl 0 cis I.459 CH₃ Clpyrimidin-2-yl CH₃ H Cl 0 cis I.460 CH₃ Cl pyrazin-2-yl CH₃ H Cl 0 cisI.461 CH₃ Cl phenyl CH₃ H Cl 0 cis I.462 CH₃ Cl methoxy CH₃ H Cl 0 cisI.463 CH₃ Cl H CH₃ H Br 2 cis I.464 CH₃ Cl Cl CH₃ H Br 2 cis I.465 CH₃Cl CH₃ CH₃ H Br 2 cis I.466 CH₃ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Br 2cis See Example 3 I.467 CH₃ Cl isoxazol-3-yl CH₃ H Br 2 cis I.468 CH₃ Cl3-methylisoxazol-5-yl CH₃ H Br 2 cis I.469 CH₃ Cl thiazol-2-yl CH₃ H Br2 cis I.470 CH₃ Cl oxazol-2-yl CH₃ H Br 2 cis I.471 CH₃ Cl 2-pyridyl CH₃H Br 2 cis I.472 CH₃ Cl pyrimidin-2-yl CH₃ H Br 2 cis I.473 CH₃ Clpyrazin-2-yl CH₃ H Br 2 cis I.474 CH₃ Cl phenyl CH₃ H Br 2 cis I.475 CH₃Cl methoxy CH₃ H Br 2 cis I.476 CH₃ Cl H CH₃ H H 2 cis I.477 CH₃ Cl ClCH₃ H H 2 cis I.478 CH₃ Cl CH₃ CH₃ H H 2 cis I.479 CH₃ Cl4,5-dihydroisoxazol-3-yl CH₃ H H 2 cis I.480 CH₃ Cl isoxazol-3-yl CH₃ HH 2 cis I.481 CH₃ Cl 3-methylisoxazol-5-yl CH₃ H H 2 cis I.482 CH₃ Clthiazol-2-yl CH₃ H H 2 cis - I.483 CH₃ Cl oxazol-2-yl CH₃ H H 2 cisI.484 CH₃ Cl 2-pyridyl CH₃ H H 2 cis I.485 CH₃ Cl pyrimidin-2-yl CH₃ H H2 cis I.486 CH₃ Cl pyrazin-2-yl CH₃ H H 2 cis I.487 CH₃ Cl phenyl CH₃ HH 2 cis I.488 CH₃ Cl methoxy CH₃ H H 2 cis I.489 CH₃ Cl H CH₃ H Cl 2trans I.490 CH₃ Cl Cl CH₃ H Cl 2 trans I.491 CH₃ Cl CH₃ CH₃ H Cl 2 transI.492 CH₃ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 trans I.493 CH₃ Clisoxazol-3-yl CH₃ H Cl 2 trans I.494 CH₃ Cl 3-methylisoxazol-5-yl CH₃ HCl 2 trans I.495 CH₃ Cl thiazol-2-yl CH₃ H Cl 2 trans I.496 CH₃ Cloxazol-2-yl CH₃ H Cl 2 trans I.497 CH₃ Cl 2-pyridyl CH₃ H Cl 2 transI.498 CH₃ Cl pyrimidin-2-yl CH₃ H Cl 2 trans I.499 CH₃ Cl pyrazin-2-ylCH₃ H Cl 2 trans I.500 CH₃ Cl phenyl CH₃ H Cl 2 trans I.501 CH₃ Clmethoxy CH₃ H Cl 2 trans I.502 CH₃ Cl H CH₃ CH₃ Cl 2 cis I.503 CH₃ Cl ClCH₃ CH₃ Cl 2 cis I.504 CH₃ Cl CH₃ CH₃ CH₃ Cl 2 cis I.505 CH₃ Cl4,5-dihydroisoxazol-3-yl CH₃ CH₃ Cl 2 cis I.506 CH₃ Cl isoxazol-3-yl CH₃CH₃ Cl 2 cis I.507 CH₃ Cl 3-methylisoxazol-5-yl CH₃ CH₃ Cl 2 cis I.508CH₃ Cl thiazol-2-yl CH₃ CH₃ Cl 2 cis I.509 CH₃ Cl oxazol-2-yl CH₃ CH₃ Cl2 cis I.510 CH₃ Cl 2-pyridyl CH₃ CH₃ Cl 2 cis I.511 CH₃ Clpyrimidin-2-yl CH₃ CH₃ Cl 2 cis I.512 CH₃ Cl pyrazin-2-yl CH₃ CH₃ Cl 2cis I.513 CH₃ Cl phenyl CH₃ CH₃ Cl 2 cis I.514 CH₃ Cl methoxy CH₃ CH₃ Cl2 cis

TABLE 2

No. R¹ R² R³ R⁴ R⁷ X n Phys. Data II.1 CH₃ Cl H CH₃ H Br 2 II.2 CH₃ ClCl CH₃ H Br 2 II.3 CH₃ Cl CH₃ CH₃ H Br 2 II.4 CH₃ Cl4,5-dihydroisoxazol-3-yl CH₃ H Br 2 II.5 CH₃ Cl isoxazol-3-yl CH₃ H Br 2II.6 CH₃ Cl 3-methylisoxazol-5-yl CH₃ H Br 2 II.7 CH₃ Cl thiazol-2-ylCH₃ H Br 2 II.8 CH₃ Cl oxazol-2-yl CH₃ H Br 2 II.9 CH₃ Cl 2-pyridyl CH₃H Br 2 II.10 CH₃ Cl pyrimidin-2-yl CH₃ H Br 2 II.11 CH₃ Cl pyrazin-2-ylCH₃ H Br 2 II.12 CH₃ Cl phenyl CH₃ H Br 2 II.13 CH₃ Cl methoxy CH₃ H Br2 II.14 CH₃ Cl H CH₃ H Cl 2 II.15 CH₃ Cl Cl CH₃ H Cl 2 II.16 CH₃ Cl CH₃CH₃ H Cl 2 II.17 CH₃ Cl 4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 see Example1 II.18 CH₃ Cl isoxazol-3-yl CH₃ H Cl 2 II.19 CH₃ Cl3-methylisoxazol-5-yl CH₃ H Cl 2 II.20 CH₃ Cl thiazol-2-yl CH₃ H Cl 2 ¹HNMR (270 MHz, CDCl₃); 8.18 (d, 1H); 7.99 (d, 1H); 7.78 (d, 1H); 7.62 (m,2H); 3.22 (s, 3H); 1.62 (s, 3H) II.21 CH₃ Cl oxazol-2-yl CH₃ H Cl 2II.22 CH₃ Cl 2-pyridyl CH₃ H Cl 2 II.23 CH₃ Cl pyrimidin-2-yl CH₃ H Cl 2II.24 CH₃ Cl pyrazin-2-yl CH₃ H Cl 2 II.25 CH₃ Cl phenyl CH₃ H Cl 2II.26 CH₃ Cl methoxy CH₃ H Cl 2 II.27 CH₃ CH₃ H CH₃ H Cl 2 II.28 CH₃ CH₃Cl CH₃ H Cl 2 II.29 CH₃ CH₃ CH₃ CH₃ H Cl 2 II.30 CH₃ CH₃4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 II.31 CH₃ CH₃ isoxazol-3-yl CH₃ H Cl2 II.32 CH₃ CH₃ 3-methylisoxazol-5-yl CH₃ H Cl 2 II.33 CH₃ CH₃thiazol-2-yl CH₃ H Cl 2 II.34 CH₃ CH₃ oxazol-2-yl CH₃ H Cl 2 II.35 CH₃CH₃ 2-pyridyl CH₃ H Cl 2 II.36 CH₃ CH₃ pyrimidin-2-yl CH₃ H Cl 2 II.37CH₃ CH₃ pyrazin-2-yl CH₃ H Cl 2 II.38 CH₃ CH₃ phenyl CH₃ H Cl 2 II.39CH₃ CH₃ methoxy CH₃ H Cl 2 II.40 CH₃CH₂ Cl H CH₃ H Br 2 II.41 CH₃CH₂ ClCl CH₃ H Br 2 II.42 CH₃CH₂ Cl CH₃ CH₃ H Br 2 II.43 CH₃CH₂ Cl4,5-dihydroisoxazol-3-yl CH₃ H Br 2 II.44 CH₃CH₂ Cl isoxazol-3-yl CH₃ HBr 2 II.45 CH₃CH₂ Cl 3-methylisoxazol-5-yl CH₃ H Br 2 II.46 CH₃CH₂ Clthiazol-2-yi CH₃ H Br 2 II.47 CH₃CH₂ Cl oxazol-2-yl CH₃ H Br 2 II.48CH₃CH₂ Cl 2-pyridyl CH₃ H Br 2 II.49 CH₃CH₂ Cl pyrimidin-2-yl CH₃ H Br 2II.50 CH₃CH₂ Cl pyrazin-2-yl CH₃ H Br 2 II.51 CH₃CH₂ Cl phenyl CH₃ H Br2 II.52 CH₃CH₂ Cl methoxy CH₃ H Br 2 II.53 CH₃CH₂ Cl H CH₃ H Cl 2 II.54CH₃CH₂ Cl Cl CH₃ H Cl 2 II.55 CH₃CH₂ Cl CH₃ CH₃ H Cl 2 II.56 CH₃CH₂ Cl4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 II.57 CH₃CH₂ Cl isoxazol-3-yl CH₃ HCl 2 II.58 CH₃CH₂ Cl 3-methylisoxazol-5-yl CH₃ H Cl 2 II.59 CH₃CH₂ Clthiazol-2-yl CH₃ H Cl 2 ¹H NMR (270 MHz, CDCl₃); 8.28 (d, 1H); 7.99 (d,1H); 7.75 (s, 1H); 7.68 (d, 1H); 4.28 (q, 2H); 3.29 (s, 3H); 1.45 (t,3H) II.60 CH₃CH₂ Cl oxazol-2-yl CH₃ H Cl 2 II.61 CH₃CH₂ Cl 2-pyridyl CH₃H Cl 2 II.62 CH₃CH₂ Cl pyrimidin-2-yl CH₃ H Cl 2 II.63 CH₃CH₂ Clpyrazin-2-yl CH₃ H Cl 2 II.64 CH₃CH₂ Cl phenyl CH₃ H Cl 2 II.65 CH₃CH₂Cl methoxy CH₃ H Cl 2 II.66 CH₃CH₂ CH₃ H CH₃ H Cl 2 II.67 CH₃CH₂ CH₃ ClCH₃ H Cl 2 II.68 CH₃CH₂ CH₃ CH₃ CH₃ H Cl 2 II.69 CH₃CH₂ CH₃4,5-dihydroisoxazol-3-yl CH₃ H Cl 2 II.70 CH₃CH₂ CH₃ isoxazol-3-yl CH₃ HCl 2 II.71 CH₃CH₂ CH₃ 3-methylisoxazol-5-yl CH₃ H Cl 2 II.72 CH₃CH₂ CH₃thiazol-2-yl CH₃ H Cl 2 II.73 CH₃CH₂ CH₃ oxazol-2-yl CH₃ H Cl 2 II.74CH₃CH₂ CH₃ 2-pyridyl CH₃ H Cl 2 II.75 CH₃CH₂ CH₃ pyrimidin-2-yl CH₃ H Cl2 II.76 CH₃CH₂ CH₃ pyrazin-2-yl CH₃ H Cl 2 II.77 CH₃CH₂ CH₃ phenyl CH₃ HCl 2 II.78 CH₃CH₂ CH₃ methoxy CH₃ H Cl 2

The compounds I and their agriculturally useful salts are suitable, bothin the form of isomer mixtures and in the form of the pure isomers, asherbicides. The herbicidal compositions comprising I control vegetationon non-crop areas very efficiently, especially at high rates ofapplication. They act against broad-leaved weeds and grass weeds incrops such as wheat, rice, maize, soya and cotton without causing anysignificant damage to the crop plants. This effect is mainly observed atlow rates of application.

Depending on the application method in question, the compounds of theformula I, or compositions comprising them, can additionally be employedin a further number of crop plants for eliminating undesirable plants.Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis,Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napusvar. napus, Brassica napus var. napobrassica, Brassica rapa var.silvestris, Camellia sinensis, Carthamus tinctorius, Caryaillinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffeacanephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucuscarota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypiumhirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypiumvitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare,Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linumusitatissimum, Lycopersicon lycopersicum, Malus spec., Manihotesculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica),Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris,Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica,Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharumofficinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum,Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

In addition, the compounds I may also be used in crops which toleratethe action of herbicides owing to breeding, including geneticengineering methods.

The active compounds or the herbicidal compositions can be applied pre-or post-emergence. If the active compounds are less well tolerated bycertain crop plants, application techniques may be used in which theherbicidal compositions are sprayed, with the aid of the sprayingequipment, in such a way that they come into as little contact aspossible, if any, with the leaves of the sensitive crop plants, whilethe active compounds reach the leaves of undesirable plants growingunderneath, or the bare soil surface (post-directed, lay-by).

The compounds I, or the herbicidal compositions comprising them, can beused for example in the form of ready-to-spray aqueous solutions,powders, suspensions, also highly-concentrated aqueous, oily or othersuspensions or dispersions, emulsions, oil dispersions, pastes, dusts,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or watering. The use forms depend on the intendeduse; in any case, they should guarantee the finest possible distributionof the active compounds according to the invention.

Suitable inert auxiliaries are essentially: mineral oil fractions ofmedium to high boiling point, such as kerosene and diesel oil,furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffin,tetrahydronaphthalene, alkylated naphthalenes and their derivatives,alkylated benzenes and their derivatives, alcohols such as methanol,ethanol, propanol, butanol and cyclohexanol, ketones such ascyclohexanone, strongly polar solvents, e.g. amines such asN-methylpyrrolidone, and water.

Aqueous use forms can be prepared from emulsion concentrates,suspensions, pastes, wettable powders or water-dispersible granules byadding water. To prepare emulsions, pastes or oil dispersions, thebenzylidenepyrazolones, either as such or dissolved in an oil orsolvent, can be homogenized in water by means of a wetting agent,tackifier, dispersant or emulsifier. Alternatively, it is possible toprepare concentrates comprising active compound, wetting agent,tackifier, dispersant or emulsifier and, if desired, solvent or oil,which are suitable for dilution with water.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, e.g. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl sulfates, lauryl ethersulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta-and octadecanols, and also of fatty alcohol glycol ether, condensates ofsulfonated naphthalene and its derivatives with formaldehyde,condensates of naphthalene, or of the naphthalenesulfonic acids withphenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylatedisooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenylpolyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, laurylalcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite wasteliquors or methylcellulose.

Powders, materials for scattering and dusts can be prepared by mixing orgrinding the active compounds together with a solid carrier.

Granules, eg. coated granules, impregnated granules and homogeneousgranules, can be prepared by binding the active ingredients to solidcarriers. Solid carriers are mineral earths, such as silicas, silicagels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers such asammonium sulfate, ammonium phosphate and ammonium nitrate, ureas, andproducts of vegetable origin, such as cereal meal, tree bark meal, woodmeal and nutshell meal, cellulose powders, or other solid carriers.

The concentrations of the active compounds I in the ready-to-usepreparations can be varied within wide ranges. In general, theformulations comprise from 0.001 to 98% by weight, preferably 0.01 to95% by weight of at least one active compound. The active compounds areemployed in a purity of from 90% to 100%, preferably 95% to 100%(according to NMR spectrum).

The formulation examples which follow illustrate the preparation of thecompounds I according to the invention:

I. 20 parts by weight of the compound No. I.20 are dissolved in amixture composed of 80 parts by weight of alkylated benzene, 10 parts byweight of the adduct of 8 to 10 mol of ethylene oxide to 1 mol of oleicacid N-monoethanolamide, 5 parts by weight of calciumdodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol ofethylene oxide to 1 mol of castor oil. Pouring the solution into 100,000parts by weight of water and finely distributing it therein gives anaqueous dispersion which comprises 0.02% by weight of the activecompound.

II. 20 parts by weight of the compound No. I.119 are dissolved in amixture composed of 40 parts by weight of cyclohexanone, 30 parts byweight of isobutanol, 20 parts by weight of the adduct of 7 mol ofethylene oxide to 1 mol of isooctylphenol and 10 parts by weight of theadduct of 40 mol of ethylene oxide to 1 mol of castor oil. Pouring thesolution into 100,000 parts by weight of water and finely distributingit therein gives an aqueous dispersion which comprises 0.02% by weightof the active compound.

III. 20 parts by weight of the active compound No. I.466 are dissolvedin a mixture composed of 25 parts by weight of cyclohexanone, 65 partsby weight of a mineral oil fraction of boiling point 210 to 280° C. and10 parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol ofcastor oil. Pouring the solution into 100,000 parts by weight of waterand finely distributing it therein gives an aqueous dispersion whichcomprises 0.02% by weight of the active compound.

IV. 20 parts by weight of the active compound No. I.20 are mixedthoroughly with 3 parts by weight of the sodium salt ofdiisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt ofa lignosulfonic acid from a sulfite waste liquor and 60 parts by weightof pulverulent silica gel, and the mixture is ground in a hammer mill.Finely distributing the mixture in 20,000 parts by weight of water givesa spray mixture which comprises 0.1% by weight of the active compound.

V. 3 parts by weight of the active compound No. I.119 are mixed with 97parts by weight of finely divided kaolin. This gives a dust whichcomprises 3% by weight of active compound.

VI. 20 parts by weight of the active compound No. I.466 are mixedintimately with 2 parts by weight of the calcium salt of thedodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycolether, 2 parts by weight of the sodium salt of aphenol/urea/formaldehyde condensate and 68 parts by weight of aparaffinic mineral oil. This gives a stable oily dispersion.

VII. 1 part by weight of the compound No. I.20 is dissolved in a mixturecomposed of 70 parts by weight of cyclo-hexanone, 20 parts by weight ofethoxylated iso-octylphenol and 10 parts by weight of ethoxylated castoroil. This gives a stable emulsion concentrate.

VIII. 1 part by weight of the compound No. I.119 is dissolved in amixture composed of 80 parts by weight of cyclohexanone and 20 parts byweight of Wettol OR [sic] EM 31 (nonionic emulsifier based onethoxylated castor oil). This gives a stable emulsion concentrate.

To widen the spectrum of action and to achieve synergistic effects, thebenzylidenepyrazolones may be mixed with a large number ofrepresentatives of other herbicidal or growth-regulating active compoundgroups and then applied concomitantly. Suitable components for mixturesare, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides,aminophosphoric acid and its derivatives, aminotriazoles, anilides,(het)aryloxyalkanoic acid and its derivatives, benzoic acid and itsderivatives, benzothiadiazinones, 2-aroyl-1,3-cyclohexanediones, hetarylaryl ketones, benzylisoxazolidinones, meta-CF₃-phenyl derivatives,carbamates, quinolinecarboxylic acid and its derivates,chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines,dichloropropionic acid and its derivatives, dihydrobenzofurans,dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers,dipyridyls, halocarboxylic acids and their derivatives, ureas,3-phenyluracils, imidazoles, imidazolinones,N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols,aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid andits derivatives, phenylpropionic acid and its derivatives, pyrazoles,phenylpyrazoles, pyridazines, pyridinecarboxylic acid and itsderivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines,triazinones, triazolinones, triazolecarboxamides and uracils.

It may furthermore be advantageous to apply the compounds I, alone or incombination with other herbicides, in the form of a mixture with othercrop protection agents, for example together with agents for controllingpests or phytopathogenic fungi or bacteria. Also of interest is themiscibility with mineral salt solutions, which are employed for treatingnutritional and trace element deficiencies. Non-phytotoxic oils and oilconcentrates may also be added.

The rates of application of active compound are from 0.001 to 3.0,preferably 0.01 to 1.0, kg/ha of active substance (a.s.), depending onthe control target, the season, the target plants and the growth stage.

Use Examples

The herbicidal activity of the benzylidenepyrazolones of the formula Iwas demonstrated by the following greenhouse experiments:

The culture containers used were plastic pots containing loamy sand withapproximately 3.0% of humus as the substrate. The seeds of the testplants were sown separately for each species.

For the pre-emergence treatment, the active compounds, which had beensuspended or emulsified in water, were applied directly after sowing bymeans of finely distributing nozzles. The containers were irrigatedgently to promote germination and growth and subsequently covered withtranslucent plastic hoods until the plants had rooted. This cover causeduniform germination of the test plants, unless this was adverselyaffected by the active compounds.

For the post-emergence treatment, the test plants were first grown to aplant height of 3 to 15 cm, depending on the plant habit, and only thentreated with the active compounds which had been suspended or emulsifiedin water. The test plants for this purpose were either sown directly andgrown in the same containers, or they were first grown separately asseedlings and transplanted into the test containers a few days prior totreatment. The rate of application for the post-emergence treatment was0.125 or 0.0625 kg/ha of a.s.

Depending on the species, the plants were kept at 10-25° C. or 20-35° C.The test period extended over 2 to 4 weeks. During this time, the plantswere tended, and their response to the individual treatments wasevaluated.

Evaluation was carried out using a scale from 0 to 100. 100 means noemergence of the plants, or complete destruction of at least the aerialparts, and 0 means no damage, or normal course of growth.

The plants used in the greenhouse experiments were from the followingspecies:

Scientific name Common name Harmful plants Chenopodium albumlambsquarters Echinochloa crus-galli barnyard grass Polygonum persicarialadys thumb Setaria faberii giant foxtail Useful plant Zea mays corn

The result showed that compound No. I.119 controls the abovementionedharmful plants very effectively (>98% damage of the plants), while theuseful plant maize was not noticeably damaged (0% damage) by thetreatment.

The comparative experiment stated in Table A shows the improvedherbicidal action of the compound I.119 according to the inventioncompared to the compound A, known from JP-A 61268670 (CA, 106: 209479).

TABLE A Post-emergence greenhouse experiments

Ex. No. I.119 A R₁ 4,5-dihydroisox- H azol-3-yl R₂ SO₂CH₃ Cl Applicationrate 0.5 0.25 0.5 0.25 (g/ha of a.s.) Test plants [damage in %]Amaranthus 100 100 40 30 retroflexus Echinochloa 100 100 80 70crus-galli Setaria faberii 100 100 10 10 Solanum nigrum 100 100 70 50

We claim:
 1. A benzylidenepyrazolone of the formula I,

where the substituents and the index n have the following meanings: R¹is unsubstituted or substituted C₁-C₆-alkyl; R² is unsubstituted orsubstituted C₁-C₆-alkyl, unsubstituted or substituted C₁-C₆-alkoxy,halogen, nitro or cyano; R³ is hydrogen, halogen, nitro, cyano, a groupNR⁵R⁶, OCOR⁵, NR⁵COR⁶, CO₂R⁵, —COSR⁵, —CONR⁵R⁶, C₁-C₄-alkoxyiminoalkyl,C₁-C₆-alkylcarbonyl, unsubstituted or substituted C₁-C₆-alkyl,unsubstituted or substituted C₁-C₆-alkoxy, unsubstituted or substitutedC₁-C₆-alkylthio, unsubstituted or substituted C₂-C₆-alkenyl,unsubstituted or substituted C₂-C₆-alkynyl, unsubstituted or substitutedphenyl, unsubstituted or substituted phenoxy, an unsubstituted orsubstituted 5- or 6-membered saturated or unsaturated heterocycle whichmay contain up to 4 nitrogen atoms and/or up to 2 oxygen or sulfur atomsas ring members; R⁴ is C₁-C₆-alkyl or C₁-C₄-haloalkyl; or R³ and R⁴ forman optionally substituted saturated or unsaturated 2- or 3-memberedbridge which may contain a sulfur atom which may be oxidized to givesulfoxide or sulfone; R⁵ is hydrogen or unsubstituted or substitutedC₁-C₆-alkyl; R⁶ is unsubstituted or substituted C₁-C₆-alkyl; R⁷ ishydrogen, C₁-C₆-alkyl or C₁-C₄-haloalkyl; n is 0, 1 or 2; X is hydrogen,chlorine or bromine; where the compounds claimed may be present both inthe trans and in the cis form or as a mixture of these isomers.
 2. Abenzylidenepyrazolone of the formula I as claimed in claim 1 in whichthe substituents have the following meanings: R¹ is C₁-C₄-alkyl orC₁-C₄-haloalkyl; R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, halogen, nitro or cyano; R³ is hydrogen, halogen,nitro, cyano, a group NR⁵R⁶, OCOR⁵, NR⁵COR⁶, CO₂R⁵, —COSR⁵, —CONR⁵R⁶,C₁-C₄-alkoxyiminoalkyl, C₁-C₄-alkylcarbonyl; the following radicals areunsubstituted or substituted by halogen, C₁-C₄-alkoxy or phenyl, wherethe phenyl ring may carry one to five substituents selected from thegroup consisting of halogen, C₁-C₂-alkyl and C₁-C₂-alkoxy: C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₂-C₆-alkenyl, C₂-C₆-alkynyl; thefollowing radicals are unsubstituted or substituted by C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy, halogen, phenyl, cyano,C₁-C₄-alkoxycarbonyl or nitro: phenyl, phenoxy, a 5- or 6-memberedsaturated or unsaturated heterocycle which may contain up to 4 nitrogenatoms and/or up to 2 oxygen or sulfur atoms as ring members; R⁵ ishydrogen, C₁-C₄-alkyl which is unsubstituted or substituted by halogen,C₁-C₄-alkoxy or phenyl, where the phenyl ring may carry one to fivesubstituents selected from the group consisting of halogen, C₁-C₂-alkyland C₁-C₂-alkoxy; R⁶ is C₁-C₄-alkyl which is unsubstituted orsubstituted by halogen, C₁-C₄-alkoxy or phenyl, where the phenyl ringmay carry one to five substituents selected from the group consisting ofhalogen, C₁-C₂-alkyl and C₁-C₂-alkoxy.
 3. A benzylidenepyrazolone of theformula I as claimed in claim 2 in which X is chlorine.
 4. Abenzylidenepyrazolone of the formula I as claimed in claim 2 in which R⁷is hydrogen.
 5. A benzylidenepyrazolone of the formula I as claimed inclaim 2 in which R² is C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy or halogen; R³ is an unsubstituted or C₁-C₄-alkyl-,C₁-C₄-alkoxy-, C₁-C₄-haloalkyl-, C₁-C₄-haloalkoxy- orhalogen-substituted 5- or 6-membered saturated or unsaturatedheterocycle selected from the group consisting of tetrahydrofuranyl,tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl,pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl,1,2,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1,2,4-triazolidinyl,1,3,4-oxadiazolidinyl, 1,3,4-thiadiazolidinyl, 1,3,4-triazolidinyl,2,3-dihydrofuranyl, 2,5-dihydrofuranyl, 2,3-dihydrothienyl,2,5-dihydrothienyl, 2,3-dihydropyrrolyl, 2,5-dihydropyrrolyl,2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl, 2,5-dihydroisoxazolyl,2,5-dihydroxazolyl, 2,3-dihydroisothiazolyl, 4,5-dihydroisothiazolyl,2,5-dihydroisothiazolyl, 2,3-dihydropyrazolyl, 4,5-dihydropyrazolyl,2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 4,5-dihydrooxazolyl,2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl, 4,5-dihydrothiazolyl,2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl, 4,5-dihydroimidazolyl,2,5-dihydroimidazolyl, morpholinyl, piperidinyl, tetrahydropyridazinyl,tetrahydropyrimidinyl, tetrahydropyrazinyl, 1,3,5-tetrahydrotriazinyl,1,2,4-tetrahydrotriazinyl, 1,3-dihydrooxazinyl, 1,3-dithianyl,tetrahydropyranyl, tetrahydrothiopyranyl, 1,3-dioxolanyl,1,1-dioxo-2,3,4,5-tetrahydrothienyl, 1,3-dihydrooxazinyl, furyl,thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl,thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl,1,2,4-triazolyl, tetrazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl,1,3,4-triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl,1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl; R⁴ is C₁-C₄-alkyl;R⁵ is hydrogen or C₁-C₄-alkyl which is unsubstituted or substituted byhalogen or C₁-C₄-alkoxy; R⁶ is C₁-C₄-alkyl which is unsubstituted orsubstituted by halogen or C₁-C₄-alkoxy; R⁷ is hydrogen; n is 2; X ishydrogen or chlorine.
 6. A composition comprising a herbicidallyeffective amount of at least one benzylidenepyrazolone of the formula Ias claimed in claim 1, and auxiliaries conventionally used in theformulation of crop protection agents.
 7. A process for preparingherbicidally active compositions as claimed in claim 6, which comprisesmixing a herbicidally effective amount of at least onebenzylidenepyrazolone I and auxiliaries conventionally used in theformulation of crop protection agents.
 8. A method for controllingunwanted vegetation, which comprises allowing a herbicidally effectiveamount of at least one benzylidenepyrazolone of the formula I as claimedin claim 1 to act on plants, their habitat and/or on seeds.
 9. A processfor preparing the benzy-lidenepyrazolone of formula I defined in claim1, which comprises reacting a benzoylpyrazolone of formula V,

with an acyl halide.
 10. The benzylidenepyrazolone defined in claim 2,wherein R¹ is C₁-C₄-alkyl.
 11. The benzylidenepyrazolone defined inclaim 2, wherein R² is C₁-C₄-alkyl.
 12. The benzylidenepyrazolonedefined in claim 2, wherein R² is methyl.
 13. The benzylidenepyrazolonedefined in claim 2, wherein R² is halogen.
 14. The benzylidenepyrazolonedefined in claim 2, wherein R² is chlorine.
 15. Thebenzylidenepyrazolone defined in claim 2, wherein R³ is hydrogen,methyl, unsubstituted benzyl or benzyl which is fluorine-, chlorine-,methyl- or methoxy-substituted in the phenyl moiety, allyl, propyn-3-yl,methoxy, ethoxy, 2-methoxyethoxy, methylthio, methylcarbonyl,methoxycarbonyl, dimethylaminocarbonyl, cyano; unsubstituted orfluorine-, chlorine- methyl- or methoxy-substituted phenyl, 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 4,5-dihydroisoxazol-3-yl, isoxazol-5-yl,isoxazol-3-yl, pyrazol-1-yl, pyrazol-5-yl, oxazol-2-yl,4,5-dihydrooxazol-2-yl, 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl,thiazol-2-yl, thiazol-5-yl, thiazol-4-yl, 1,2,4-triazol-1-yl,1,3,4-oxadiazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidin-2-yl,pyrimidin-4-yl, 1,3-dioxan-2-yl or 1,3-dithian-2-yl.
 16. Thebenzylidenepyrazolone defined in claim 2, wherein R³ is unsubstituted orfluorine-, chlorine-, methyl- or methoxy-substituted phenyl, 2-furyl,3-furyl, 2-thienyl, 3-thienyl, 4,5-dihydroisoxazol-3-yl, isoxazol-5-yl,isoxazol-3-yl, pyrazol-1-yl, pyrazol-5-yl, oxazol-2-yl,4,5-dihydrooxazol-2-yl, 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl,thiazol-2-yl, thiazol-5-yl, thiazol-4-yl, 1,2,4-triazol-1-yl,1,3,4-oxadiazol-2-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, pyrimidin-2-yl,pyrimidin-4-yl, 1,3-dioxan-2-yl or 1,3-dithian-2-yl.
 17. Thebenzylidenepyrazolone defined in claim 2, wherein R³ is unsubstituted offluorine-, chlorine-, methyl- or methoxy-substituted4,5-dihydroisoxazol-3-yl, isoxazol-5-yl or isoxazol-3-yl.
 18. Thebenzylidenepyrazolone defined in claim 2, wherein n is two.
 19. Thebenzylidenepyrazolone defined in claim 2, wherein R⁴ is C₁-C₄-alkyl. 20.The benzylidenepyrazolone defined in claim 2, wherein R⁷ is hydrogen.21. The benzylidenepyrazolone defined in claim 2, wherein R² and R⁴ areC₁-C₄-alkyl groups, R³ is an unsubstituted or fluorine-, chlorine-,methyl- or methoxy-substituted 4,5-dihydroisoxazol-3-yl, isoxazol-5-ylor isoxazol-3-yl group, n denotes two, and X is chlorine.